Title

"Effect of anion and ligand ratio in selfassembled silver(!) complexes of 4-(diphenylphosphinomethyl)pyridine and their derivatives with bipyridine ligands

Document Type

Article

Publication Date

2009

Abstract

An efficient procedure for the synthesis of the novel bidentate ligand 4-(diphenylphosphinomethyl)pyridine (PMP-41, 1) has been developed and its coordination behavior with Ag(I) has been studied. Reaction of the PMP-41 ligand with the silver(I) salts of tetrafluoroborate (BF4-)" role="presentation" style="box-sizing: border-box; margin: 0px; padding: 0px; display: inline-block; line-height: normal; font-size: 14.4px; word-spacing: normal; word-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; position: relative;">(BF4-), trifluoromethanesulfonate (Otf−), and trifluoroacetate (tfa−) produces discrete molecules and polymeric structures that depend on the varying degrees of interaction of the corresponding anion with the metal centers. When the proportion of ligand to metal is 1:1, a bimetallic box conformation is obtained with AgBF4 and AgOtf (2 and 5, respectively). Varying the ratio to 2:1, a polymeric chain of bimetallic boxes is constructed when the BF4-" role="presentation" style="box-sizing: border-box; margin: 0px; padding: 0px; display: inline-block; line-height: normal; font-size: 14.4px; word-spacing: normal; word-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; position: relative;">BF4- salt is used (3). With Agtfa two distinct structural motifs are formed (8A and 8B), arising from the crystallization process of using two different solvent systems. Further reaction of the AgBF4/PMP-41 and AgOtf/PMP-41 adducts with the chelating 5,5′-dimethyl-2,2′-bipyridine or the bridging 4,4′-bipyridine ligands affords dimeric and bridged structural motifs, depending upon the coordination ability of the corresponding bipyridine fragment. Addition of the 5,5′-dimethyl-2,2′-bipyridine ligand to a solution containing AgBF4 and PMP-41 results the capping of the silver atoms by the bipyridine fragment 4, and the disruption of the bimetallic box in the AgOtf(PMP-41) structure to generate an infinite chain in a 1:1:1 ratio of the reactants 6. As expected, the 4,4′-bipyridine acts as a bridging ligand by connecting [AgOtf(PMP-41)]2 molecules, which results in the formation of compound 7. Low-temperature luminescence spectra were also collected for all compounds and are compared.

DOI

10.1016/j.ica.2008.04.032

Comments

Hung-Low, F.; Klausmeyer, K. K.; Gary, J . B. "Effect of anion and ligand ratio in selfassembled silver(!) complexes of 4-(diphenylphosphinomethyl)pyridine and their derivatives with bipyridine ligands." lnorg. Chim. Acta. 2009, 362, 426-436.

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